CN116555907B - Preparation method of bionic self-cleaning polycrystalline diamond - Google Patents
Preparation method of bionic self-cleaning polycrystalline diamond Download PDFInfo
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 135
- 239000010432 diamond Substances 0.000 title claims abstract description 135
- 238000004140 cleaning Methods 0.000 title claims abstract description 35
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 48
- 238000005530 etching Methods 0.000 claims abstract description 47
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002113 nanodiamond Substances 0.000 claims abstract description 9
- 238000007385 chemical modification Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000428 dust Substances 0.000 abstract description 15
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 9
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 17
- 230000002209 hydrophobic effect Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 240000002853 Nelumbo nucifera Species 0.000 description 4
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 4
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 210000001595 mastoid Anatomy 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/04—Diamond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/12—Production of homogeneous polycrystalline material with defined structure directly from the gas state
- C30B28/14—Production of homogeneous polycrystalline material with defined structure directly from the gas state by chemical reaction of reactive gases
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/12—Etching in gas atmosphere or plasma
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of bionic self-cleaning polycrystalline diamond, and aims to solve the problem that dust is easy to adsorb on the surface of polycrystalline diamond. The preparation method comprises the following steps: 1. ultrasonically cleaning the polycrystalline diamond; 2. diamond is put into chemical vapor deposition equipment; 3. introducing reaction gases H 2 and O 2 to keep the surface temperature of the diamond at 500-900 ℃ for oxygen etching for 1-3H; 4. ar, N 2 and CH 4 are introduced to carry out the epitaxial growth of the nano diamond for 0.5 to 3 hours; 5. h 2 is introduced to keep the surface temperature of the diamond between 500 and 900 ℃ for hydrogen etching for 1 to 3 hours; 6. closing the device; 7. and dripping fluorosilane to carry out surface chemical modification. According to the invention, three-step methods are adopted to respectively perform oxygen etching, epitaxial growth and hydrogen etching on the diamond, so that a double micro-nano structure with high specific surface area is formed on the surface of the polycrystalline diamond, the super-hydrophobic property of the surface of the polycrystalline diamond is realized, and the self-cleaning function is excellent.
Description
Technical Field
The invention belongs to the field of superhard materials, and particularly relates to a preparation method of bionic self-cleaning polycrystalline diamond applied to the fields of material science, physical chemistry, geological drilling and the like.
Background
The diamond is an atomic crystal which is completely composed of carbon in an sp 3 structure, has the highest hardness and heat conductivity coefficient in nature, has ultra-wide band gap of 4.5eV and radiation resistance, has ultra-wide transmittance from far infrared to ultraviolet, and is commonly used for drills, cutting edges, radiating substrates, special environment windows, protective coatings and the like. However, the diamond in the atmospheric environment is usually adsorbed with impurities such as carbon, oxygen and the like on the surface, so that the diamond surface energy is usually high, the diamond has hydrophilic and oleophilic characteristics, and the diamond terminated by oxygen has a positron affinity surface, so that dust with natural negative charges is easily adsorbed.
The adsorption force of the solid surface on dust and water is classified into van der waals force, electrostatic force and capillary force, and the solid surface energy, roughness and charge state are related. Generally, the lower the surface energy, the less prone to adsorption of water and dust; while a rough surface can cause gaps between the droplets and the solid surface, making the solid surface difficult to wet; meanwhile, the roughness increases the contact distance between dust and the solid surface, and reduces the van der Waals force between the dust and the solid surface. The self-cleaning function of the lotus leaf is caused by a double micro-nano structure consisting of a micron-sized mastoid structure on the surface and a nano-sized waxy microneedle on the surface of the mastoid structure, so that the lotus leaf has a natural hydrophobic effect, and can keep the effect of 'getting silt but not dyeing' even if dirt is adhered to the lotus leaf and washed by water.
The hydrophobicity of a solid surface is measured by the hydrophobic angle. When the liquid drops on the solid surface and reaches a stable state, the surface tension of the solid-liquid-gas three phases reaches balance, and at the moment, the three-phase contact point corresponds to the included angle (theta) between the tangent line of the liquid surface and the solid surface, namely the contact angle theta of the solid surface. When the contact angle of the solid surface with water is smaller than 90 degrees, the solid surface is considered to have hydrophilicity; when the contact angle of the solid surface with water is more than 90 degrees, the solid surface is considered to have hydrophobicity; whereas when the contact angle is greater than 150 ° and the rolling angle is less than 10 °, the solid surface exhibits superhydrophobicity. A solid surface with superhydrophobic self-cleaning function should have a small rolling angle (< 10 °) in addition to a high contact angle (> 150 °), the rolling angle being defined as the inclination angle of the bottom solid when the liquid beads are about to roll under gravity.
Disclosure of Invention
The invention aims to solve the problem that dust is easy to adsorb on the surface of polycrystalline diamond, and provides a preparation method of polycrystalline diamond with a bionic self-cleaning function, so that the polycrystalline diamond has a micro-nano structure similar to the surface of lotus leaf and a self-cleaning function of being hydrophobic and not sticky with dust.
The preparation method of the bionic self-cleaning polycrystalline diamond is realized according to the following steps:
1. sequentially carrying out ultrasonic cleaning on polycrystalline diamond or polycrystalline diamond by using acetone, ethanol and deionized water to obtain cleaned diamond;
2. placing the cleaned diamond into a cavity of a Chemical Vapor Deposition (CVD) device;
3. After vacuumizing a cavity of the chemical vapor deposition equipment, introducing reaction gases H 2 and O 2, controlling the flow rate of H 2 to be 100 sccm-400 sccm, controlling the flow rate of O 2 to be 2% -10% of the total gas flow rate, gradually increasing the air pressure and power after starting the chemical vapor deposition equipment, keeping the surface temperature of the diamond at 500-900 ℃, and performing oxygen etching for 1-3 hours to obtain the diamond after oxygen etching;
4. Closing H 2 and O 2, introducing Ar, N 2 and CH 4 for gas replacement, controlling the Ar flow to be 20-200 sccm, the Ar flow to be 65-75% of the total gas flow, controlling the N 2 flow to be 20-30% of the total gas flow, and the CH 4 flow to be 5-10% of the total gas flow, so that the surface temperature of the diamond is kept between 500 and 900 ℃, and performing epitaxial growth of the nano diamond for 0.5-3H to obtain the diamond after epitaxial growth;
5. Closing Ar, N 2 and CH 4, then introducing H 2 for gas replacement, controlling the flow rate of H 2 to be 100 sccm-400 sccm, keeping the surface temperature of the diamond at 500-900 ℃, and performing hydrogen etching for 1-3H to obtain the diamond after hydrogen etching;
6. Gradually reducing the air pressure and the power, keeping the flow of H 2 during the temperature reduction until the chemical vapor deposition equipment is closed, and taking out the grown and etched diamond;
7. Placing the grown and etched diamond in a closed container, dripping fluorosilane into the container, heating at the constant temperature of 90-150 ℃ for 0.5-3 h to carry out surface chemical modification, and obtaining the bionic self-cleaning polycrystalline diamond.
The micro-nano dual roughness prepared by the method can respectively etch the diamond by oxygen in a three-step method in a diamond CVD device to form micro-scale grain protrusions, then grow nano-diamond to form nano-scale protrusions, then etch by hydrogen to form nano-needles with higher specific surface area, and then further reduce the surface energy by using the chemical modification of the fluorosilane surface after being taken out. The three steps of etching, growing and etching are completed by replacing working gas in one device, the super-hydrophobic surface is constructed on the polycrystalline diamond, a nano column/needle mask is not required to be prepared, special etching devices such as ICP and the like are avoided to be additionally used, the operation complexity is reduced, the production cost is reduced, and compared with the super-hydrophobic surface prepared by a coating method such as nano SiO 2 pellets, polymer and the like, the super-hydrophobic surface has higher wear resistance and longer service life.
Drawings
FIG. 1 is a hydrophobic angle of a pristine diamond film, 24 indicating that untreated diamond is hydrophilic;
FIG. 2 is a photograph of the hydrophobic angle of the diamond film on the diamond after the growth etching obtained in the step six of example 1;
FIG. 3 is a photograph of the hydrophobic angle of the diamond film on the biomimetic self-cleaning polycrystalline diamond obtained in step seven of example 1;
FIG. 4 is an electron microscope image of micron-sized protrusions on the diamond surface after oxygen etching in example 1;
FIG. 5 is an electron microscope image of nano-scale protrusions on the diamond surface after hydrogen etching in example 1;
FIG. 6 is a photograph of polycrystalline diamond subjected to an etching-growth-etching three-step process after dust is scattered from the surface, the dashed box shows that this region is modified with fluorosilane, while other regions are not surface chemically modified;
Fig. 7 is a photograph of polycrystalline diamond with surface dust dithered away;
Fig. 8 is a photograph of polycrystalline diamond after dust has been flushed with a water stream.
Detailed Description
The first embodiment is as follows: the preparation method of the bionic self-cleaning polycrystalline diamond in the embodiment is implemented according to the following steps:
1. sequentially carrying out ultrasonic cleaning on polycrystalline diamond or polycrystalline diamond by using acetone, ethanol and deionized water to obtain cleaned diamond;
2. placing the cleaned diamond into a cavity of a Chemical Vapor Deposition (CVD) device;
3. After the cavity of the chemical vapor deposition equipment is vacuumized, introducing reaction gases H 2 and O 2, controlling the flow of H 2 to be 100 sccm-400 sccm, controlling the flow of O 2 to be 2% -10% of the total gas flow, gradually increasing the air pressure and power after the chemical vapor deposition equipment is started, keeping the surface temperature of the diamond at 500-900 ℃, and performing oxygen etching for 1-3 hours to obtain the diamond after oxygen etching. The etching capability of oxygen on carbon is very strong, sp 2 impurities among diamond grain boundaries can be oxidized, and irregular micron-sized protrusions and recesses are etched on the surfaces of diamond grains;
4. Closing H 2 and O 2, introducing Ar, N 2 and CH 4 for gas replacement, controlling the Ar flow to be 20-200 sccm, the Ar flow to be 65-75% of the total gas flow, controlling the N 2 flow to be 20-30% of the total gas flow, and the CH 4 flow to be 5-10% of the total gas flow, so that the surface temperature of the diamond is kept between 500-900 ℃, carrying out epitaxial growth of nano-diamond on the micron-sized diamond bulge after oxygen etching, and growing for 0.5-3H to obtain epitaxially grown diamond, wherein the grain size of the diamond is nano-sized;
5. Closing Ar, N 2 and CH 4, then introducing H 2 for gas replacement, controlling the flow rate of H 2 to be 100 sccm-400 sccm, keeping the surface temperature of the diamond at 500-900 ℃, and performing hydrogen etching for 1-3H to obtain the diamond after hydrogen etching; the etching capability of hydrogen to carbon is weaker than that of oxygen, and besides etching grain boundary impurities, nano-crystals can be etched to form nano-scale protrusions;
6. Gradually reducing the air pressure and the power, keeping the flow of H 2 during the temperature reduction until the chemical vapor deposition equipment is closed, and taking out the grown and etched diamond;
7. placing the grown and etched diamond in a closed container, dripping fluorosilane into the container, heating at the constant temperature of 90-150 ℃ for 0.5-3h to evaporate the fluorosilane, and carrying out surface chemical modification on the diamond to obtain the bionic self-cleaning polycrystalline diamond.
The fluorosilane in the seventh embodiment can reduce the surface energy of diamond, so that the adsorption capability of the fluorosilane to micro droplets and dust is further weakened.
The second embodiment is as follows: the difference between the present embodiment and the specific embodiment is that the time of ultrasonic cleaning in the first step is 10-20 min.
And a third specific embodiment: the difference between the present embodiment and the first or second embodiment is that in the third step, the flow rate of H 2 is controlled to be 200sccm to 300sccm, and the flow rate of o 2 is 2% of the total gas flow rate.
The specific embodiment IV is as follows: the difference between the present embodiment and one to three embodiments is that in the third step, the surface temperature of the diamond is kept at 800 ℃ and oxygen etching is performed for 2 hours.
Fifth embodiment: the present embodiment differs from the first to fourth embodiments in that the flow rate of Ar is controlled to be 50 to 100sccm in the fourth step.
Specific embodiment six: the fifth difference between the present embodiment and the fifth embodiment is that in the fourth step, the Ar flow is controlled to 70% of the total gas flow, the N 2 flow is controlled to 25% of the total gas flow, and the CH 4 flow is controlled to 5% of the total gas flow.
Seventh embodiment: the sixth embodiment is different from the sixth embodiment in that in the fourth step, the surface temperature of the diamond is kept between 800 and 900 ℃ and the epitaxial growth of the nanodiamond is performed for 1 to 2 hours.
Eighth embodiment: the difference between the present embodiment and one of the first to seventh embodiments is that in the fifth step, the flow rate of H 2 is controlled to be 200sccm.
Detailed description nine: in the fifth embodiment, the temperature of the diamond surface is maintained at 800 to 900 ℃ and hydrogen etching is performed for 2 to 2.5 hours, which is different from the eighth embodiment.
Detailed description ten: the difference between the embodiment and one to nine embodiments is that in the seventh step, the surface is chemically modified by heating for 1 to 1.5 hours at a constant temperature of 100 to 120 ℃.
Example 1: the preparation method of the bionic self-cleaning polycrystalline diamond is implemented according to the following steps:
1. Sequentially carrying out ultrasonic cleaning on polycrystalline diamond by using acetone, ethanol and deionized water to obtain cleaned diamond;
2. placing the cleaned diamond into a cavity of a Chemical Vapor Deposition (CVD) device;
3. After vacuumizing a cavity of the chemical vapor deposition equipment, introducing reaction gases H 2 and O 2, controlling the flow rate of H 2 to be 200sccm and the flow rate of O 2 to be 2% of the total gas flow rate, starting the chemical vapor deposition equipment, gradually increasing the power to 3000W, increasing the air pressure to 60torr, keeping the surface temperature of the diamond at 800 ℃, and performing oxygen etching for 2 hours to obtain oxygen etched diamond;
4. closing H 2 and O 2, introducing Ar, N 2 and CH 4 for gas replacement, controlling the Ar flow to 70sccm, the Ar flow to 70% of the total gas flow, controlling the N 2 flow to 25% of the total gas flow, and the CH 4 flow to 5% of the total gas flow, so that the surface temperature of the diamond is kept at 850 ℃, and carrying out epitaxial growth of the nano diamond for 1H to obtain the diamond after epitaxial growth;
5. Closing Ar, N 2 and CH 4, then introducing H 2 for gas replacement, controlling the flow rate of H 2 to be 200sccm, keeping the surface temperature of the diamond at 800 ℃, and performing hydrogen etching for 2 hours to obtain the diamond after hydrogen etching;
6. Gradually reducing the air pressure and the power, keeping the flow of H 2 during the temperature reduction until the chemical vapor deposition equipment is closed, and taking out the grown and etched diamond;
7. And placing the grown and etched diamond in a closed container, dripping fluorosilane into the container, and heating at the constant temperature of 100 ℃ for 1h to carry out surface chemical modification to obtain the bionic self-cleaning polycrystalline diamond.
The bionic self-cleaning polycrystalline diamond is prepared in the embodiment, and is shown in figure 3. The contact angle of the water drop with the surface of 5 mu L can reach 152.3 degrees, and the level of super-hydrophobicity is achieved. And step six, the hydrophobic angle of the diamond film after the three-step etching-growing-etching method is 120.4 degrees, and the diamond film is hydrophobic.
The three steps of etching, growing and etching are completed by replacing working gas in one device, a nano column/needle mask is not required to be prepared, special etching devices such as ICP (inductively coupled plasma) and the like are avoided, the operation complexity is reduced, the production cost is reduced, and compared with the super-hydrophobic surface prepared by a coating method such as nano SiO 2 pellets, polymer and the like, the super-hydrophobic surface has higher wear resistance and longer service life.
Example 2: the preparation method of the bionic self-cleaning polycrystalline diamond is implemented according to the following steps:
1. Sequentially carrying out ultrasonic cleaning on polycrystalline diamond by using acetone, ethanol and deionized water to obtain cleaned diamond;
2. placing the cleaned diamond into a cavity of a Chemical Vapor Deposition (CVD) device;
3. After vacuumizing a cavity of the chemical vapor deposition equipment, introducing reaction gases H 2 and O 2, controlling the flow rate of H 2 to be 200sccm and the flow rate of O 2 to be 5% of the total gas flow rate, starting the chemical vapor deposition equipment, gradually increasing the power to 4000W, increasing the air pressure to 80torr, keeping the surface temperature of the diamond at 600 ℃, and performing oxygen etching for 2 hours to obtain oxygen etched diamond;
4. Closing H 2 and O 2, introducing Ar, N 2 and CH 4 for gas replacement, controlling the Ar flow to 28sccm, the Ar flow to 70% of the total gas flow, controlling the N 2 flow to 25% of the total gas flow, and the CH 4 flow to 5% of the total gas flow, so that the surface temperature of the diamond is kept at 700 ℃, and carrying out epitaxial growth of the nano diamond for 1H to obtain the diamond after epitaxial growth;
5. closing Ar, N 2 and CH 4, then introducing H 2 for gas replacement, controlling the flow rate of H 2 to be 200sccm, keeping the surface temperature of the diamond at 700 ℃, and performing hydrogen etching for 2 hours to obtain the diamond after hydrogen etching;
6. Gradually reducing the air pressure and the power, keeping the flow of H 2 during the temperature reduction until the chemical vapor deposition equipment is closed, and taking out the grown and etched diamond;
7. and placing the grown and etched diamond in a closed container, dripping fluorosilane into the container, and heating at the constant temperature of 140 ℃ for 1h to carry out surface chemical modification to obtain the bionic self-cleaning polycrystalline diamond.
The bionic self-cleaning polycrystalline diamond is prepared in the embodiment, the self-cleaning function test is shown in figures 6-8, dust is scattered on the surface of the polycrystalline diamond through the three-step method of etching, growing and etching, a broken line frame shows that the region is decorated by fluorosilane, and other regions are not subjected to surface chemical decoration; after shaking, dust on the region of the polycrystalline diamond surface decorated by the fluorosilane almost falls off, and a small part of the region which is not decorated by the fluorosilane still adheres; but all dust falls off after water flow flushing, which shows that the polycrystalline diamond subjected to the etching-growing-etching three-step method and the fluorosilane chemical surface modification has an excellent self-cleaning function.
The three steps of etching, growing and etching are completed by only replacing working gas in one device, a nano column/needle mask is not needed to be prepared, special etching devices such as ICP and the like are avoided to be additionally used, the operation complexity is reduced, the production cost is reduced, and compared with the super-hydrophobic surface prepared by a coating method such as nano SiO 2 pellets, polymer and the like, the super-hydrophobic surface has higher wear resistance and longer service life.
Polycrystalline diamond is commonly used as superhard material for precision machining and geological drilling, and the self-cleaning function can prevent a great amount of chips from adhering to the surface of the polycrystalline diamond bit when a workpiece is cut to influence heat dissipation and cutting performance, and can also prevent the polycrystalline diamond bit from sticking during geological drilling, so that the service life of the polycrystalline diamond bit or a drilling tool is prolonged, and the due performance of diamond is exerted.
Claims (10)
1. The preparation method of the bionic self-cleaning polycrystalline diamond is characterized by comprising the following steps of:
1. sequentially carrying out ultrasonic cleaning on polycrystalline diamond or polycrystalline diamond by using acetone, ethanol and deionized water to obtain cleaned diamond;
2. placing the cleaned diamond into a cavity of chemical vapor deposition equipment;
3. After vacuumizing a cavity of the chemical vapor deposition equipment, introducing reaction gases H 2 and O 2, controlling the flow rate of H 2 to be 100 sccm-400 sccm, controlling the flow rate of O 2 to be 2% -10% of the total gas flow rate, gradually increasing the air pressure and power after starting the chemical vapor deposition equipment, keeping the surface temperature of the diamond at 500-900 ℃, and performing oxygen etching for 1-3 hours to obtain the diamond after oxygen etching;
4. Closing H 2 and O 2, introducing Ar, N 2 and CH 4 for gas replacement, controlling the Ar flow to be 20-200 sccm, the Ar flow to be 65-75% of the total gas flow, controlling the N 2 flow to be 20-30% of the total gas flow, and the CH 4 flow to be 5-10% of the total gas flow, so that the surface temperature of the diamond is kept between 500 and 900 ℃, and performing epitaxial growth of the nano diamond for 0.5-3H to obtain the diamond after epitaxial growth;
5. Closing Ar, N 2 and CH 4, then introducing H 2 for gas replacement, controlling the flow rate of H 2 to be 100 sccm-400 sccm, keeping the surface temperature of the diamond at 500-900 ℃, and performing hydrogen etching for 1-3H to obtain the diamond after hydrogen etching;
6. Gradually reducing the air pressure and the power, keeping the flow of H 2 during the temperature reduction until the chemical vapor deposition equipment is closed, and taking out the grown and etched diamond;
7. Placing the grown and etched diamond in a closed container, dripping fluorosilane into the container, heating at the constant temperature of 90-150 ℃ for 0.5-3 h to carry out surface chemical modification, and obtaining the bionic self-cleaning polycrystalline diamond.
2. The method for preparing the bionic self-cleaning polycrystalline diamond according to claim 1, wherein the ultrasonic cleaning time in the first step is 10-20 min each time.
3. The method for preparing the bionic self-cleaning polycrystalline diamond according to claim 1, wherein in the third step, the flow rate of H 2 is controlled to be 200 sccm-300 sccm, and the flow rate of O 2 is controlled to be 2% of the total gas flow rate.
4. The method of fabricating a bionic self-cleaning polycrystalline diamond according to claim 1, wherein in the third step, the surface temperature of the diamond is maintained at 800 ℃, and oxygen etching is performed for 2 hours.
5. The method for preparing the bionic self-cleaning polycrystalline diamond according to claim 1, wherein the Ar flow is controlled to be 50-100 sccm in the fourth step.
6. The method of fabricating a bionic self-cleaning polycrystalline diamond according to claim 1, wherein in the fourth step, the flow rate of Ar is controlled to 70% of the total gas flow rate, the flow rate of N 2 is controlled to 25% of the total gas flow rate, and the flow rate of CH 4 is controlled to 5% of the total gas flow rate.
7. The method for preparing a bionic self-cleaning polycrystalline diamond according to claim 1, wherein in the fourth step, the surface temperature of the diamond is kept between 800 ℃ and 900 ℃ and epitaxial growth of the nano diamond is carried out for 1 to 2 hours.
8. The method for preparing the bionic self-cleaning polycrystalline diamond according to claim 1, wherein in the fifth step, the flow rate of H 2 is controlled to be 200sccm.
9. The method for preparing the bionic self-cleaning polycrystalline diamond according to claim 1, wherein in the fifth step, the surface temperature of the diamond is kept between 800 ℃ and 900 ℃ and hydrogen etching is carried out for 2 to 2.5 hours.
10. The method for preparing the bionic self-cleaning polycrystalline diamond according to claim 1, wherein the surface chemical modification is performed by heating for 1-1.5 hours at the constant temperature of 100-120 ℃ in the seventh step.
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